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Method for synthesizing 1,2-dissubstituted olefin compounds by alkyne alkylation

A compound and disubstitution technology, applied in the field of synthesis of organic compounds, can solve problems such as addition that has not been reported, and achieve high stereoselectivity, high yield, and low toxicity

Active Publication Date: 2019-12-13
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above two cases are the addition of aldehydes as alkylating agents to alkenes, and the hydroxyl or amine part is retained, while the addition of aldehydes as alkylating agents to alkynes has not been reported.

Method used

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  • Method for synthesizing 1,2-dissubstituted olefin compounds by alkyne alkylation
  • Method for synthesizing 1,2-dissubstituted olefin compounds by alkyne alkylation
  • Method for synthesizing 1,2-dissubstituted olefin compounds by alkyne alkylation

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038]

[0039] The photosensitizer PS3 (0.01mmol, 11.5mg), 4-phenylphenylacetylene (0.2mmol, 35.6mg), Hans ester (0.24mmol, 60.8mg) was added to a dry Schlenk reaction tube, and the nitrogen gas was replaced three times. Under nitrogen protection, butyraldehyde (1.0 mmol, 72.1 mg) and diethylamine (1.0 mmol, 73.1 mg) in acetonitrile (4 mL) were added, and the reaction tube was stirred for 12 hours under 15W blue LED irradiation. After the reaction was completed, 100-200 mesh column chromatography silica gel was added to the obtained reaction solution and the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to silica gel column chromatography separation, and eluted with petroleum ether as an eluent, followed by TLC. In the elution process, collect the eluent containing the target product, combine the eluents and evaporate the solvent to obtain the pure product. The material was a colorless liquid, 15% yield, E / Z=10 / 1 of the prod...

Embodiment 2

[0045]

[0046] The photosensitizer PS4 (0.01mmol, 10.5mg), phenylacetylene (0.2mmol, 20.4mg), Hans ester (0.24mmol, 60.8mg) was added to the dry Schlenk reaction tube, filled with nitrogen three times, under the protection of nitrogen Butyraldehyde (1.0 mmol, 72.1 mg) and diethylamine (1.0 mmol, 73.1 mg) in acetonitrile (4 mL) were added, and the reaction tube was stirred for 12 hours under 15W blue LED irradiation. After the reaction was completed, 100-200 mesh column chromatography silica gel was added to the obtained reaction solution and the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to silica gel column chromatography separation, and eluted with petroleum ether as an eluent, followed by TLC. In the elution process, collect the eluent containing the target product, combine the eluents and evaporate the solvent to obtain the pure product. The material was a colorless liquid, yield 14%, E / Z=10 / 1 of the product.

[0047...

Embodiment 3

[0049]

[0050] The photosensitizer PS5 (0.01mmol, 12.0mg), 4-bromophenylacetylene (0.2mmol, 36.2mg), Hans ester (0.24mmol, 60.8mg) was added to the dry Schlenk reaction tube, and the nitrogen gas was replaced three times. Under nitrogen protection, butyraldehyde (1.0 mmol, 72.1 mg) and diethylamine (1.0 mmol, 73.1 mg) in acetonitrile (4 mL) were added, and the reaction tube was placed under 15W blue LED irradiation and stirred for 12 hours. After the reaction was completed, 100-200 mesh column chromatography silica gel was added to the obtained reaction solution and the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to silica gel column chromatography separation, and eluted with petroleum ether as an eluent, followed by TLC. In the elution process, collect the eluent containing the target product, combine the eluents and evaporate the solvent to obtain the pure product. The material was a colorless liquid, 27% yield, E / Z=11 / 1...

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Abstract

The invention discloses a method for synthesizing 1,2-dissubstituted olefin compounds by high-selectivity alkyne alkylation. The method comprises the following specific steps: a photosensitizer, an alkyne compound represented as the formula I and hantzsch ester are added to a Schlenk reaction tube, aldehyde represented as the formula II and secondary amine are dissolved in an organic solvent or amixed solvent of 1,4-dioxane and water under protective gas atmosphere, a mixed solution is obtained, the mixed solution is added to the Schlenk reaction tube under the condition of protective gas andis stirred for a reaction at 25 DEG C for 6-14 h, preferably 12 h under the irradiation of a light source, and the 1,2-dissubstituted olefin compounds represented as the formula III are obtained after the obtained reaction solution is subjected to aftertreatment. Polysubstituted alkenes which are difficult to prepare with the conventional method can be synthesized with the method, and the methodhas the advantages of being high in reaction stereoselectivity, relatively mild in reaction condition, high in yield, high in substrate universality and simple and convenient to operate, a catalyst ischeap and available and has lower toxicity, and energy consumption is reduced.

Description

[0001] (1) Technical field [0002] The invention relates to a method for synthesizing organic compounds, in particular to a method for synthesizing 1,2-disubstituted olefin compounds. [0003] (2) Background technology [0004] Olefins are one of the most important and basic organic compounds. Olefin modules are commonly found in various biological common drugs and natural products, and are also widely used in the field of materials. In addition, olefins are the most commonly used intermediates in organic synthesis, and can undergo a series of reactions such as polymerization, olefin metathesis, epoxidation, hydroformylation, and hydroamination. Therefore, the research and development of related synthesis technologies of olefinic compounds has broad application prospects. Although since the last century, chemists at home and abroad have developed a variety of efficient and versatile methods for synthesizing olefins, the classic ones are witting reaction, Peterson reaction, Ta...

Claims

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Application Information

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IPC IPC(8): C07C2/74C07C15/50C07C15/44C07C15/58C07C17/272C07C25/24C07C22/04C07C253/30C07C255/50C07C67/343C07C69/76C07C315/04C07C317/14C07C41/30C07C43/215C07C67/293C07C69/78C07C231/12C07C233/65C07D333/08C07D213/16C07D213/127C07D333/54C07D211/16
CPCC07C2/74C07C17/272C07C253/30C07C67/343C07C69/76C07C315/04C07C41/30C07C67/293C07C231/12C07D333/08C07D213/16C07D213/127C07D333/54C07D211/16C07B2200/07C07C15/50C07C15/44C07C15/58C07C25/24C07C22/04C07C255/50C07C317/14C07C43/215C07C69/78C07C233/65
Inventor 刘运奎鲍汉扬郑立孟
Owner ZHEJIANG UNIV OF TECH
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